US6358447B1 - Process for the production of a positive electrode for an alkaline primary element - Google Patents

Process for the production of a positive electrode for an alkaline primary element Download PDF

Info

Publication number
US6358447B1
US6358447B1 US09429809 US42980999A US6358447B1 US 6358447 B1 US6358447 B1 US 6358447B1 US 09429809 US09429809 US 09429809 US 42980999 A US42980999 A US 42980999A US 6358447 B1 US6358447 B1 US 6358447B1
Authority
US
Grant status
Grant
Patent type
Prior art keywords
process
graphite
organic polymer
weight
form
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09429809
Inventor
Jose Horst-Udo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Varta Geratebatterie GmbH
Original Assignee
Varta Geratebatterie GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0473Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals
    • H01M4/0478Filling tube-or pockets type electrodes; Applying active mass in cup-shaped terminals with dispersions, suspensions or pastes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/06Electrodes for primary cells
    • H01M4/08Processes of manufacture

Abstract

The invention relates to a process for producing a positive electrode, containing an organic polymer as binder, for primary elements with alkaline electrolytes. The process according to the invention is carried out in the following way: manganese dioxide particles are mixed with a graphite dispersion, which contains an organic polymer, and are compressed to form an electrode body.

Description

FIELD OF THE INVENTION

The invention relates to a process for producing a positive electrode, containing an organic polymer as a binder, for primary elements with alkaline electrolytes.

BACKGROUND OF THE INVENTION

The electrode mass for the positive electrode is compressed to form cylindrical shaped parts for the production of alkaline primary elements of the mass type. The main constituents of the electrode mass are manganese dioxide and a highly conductive graphite which improves the electronic conductivity of the electrode. Many producers add 4 to 8% by weight of aqueous potassium hydroxide solution (KOH) to the electrode mass for the positive electrode of alkaline primary elements. Molded articles produced from this mixture using commercially available machines need, in addition to the electrochemical requirements, to meet minimum requirements in terms of dimensional stability and mechanical strength to guarantee that they can be processed without problems in mass production. A binder is often added to the electrode mass for this purpose. Although adding amounts of KOH solution does lead to adhesive consolidation of the particles of the mass, it also causes a disproportionately high degree of wear on the pressing tools as well.

The literature discloses a number of polymeric binders, which are added to the electrode mass as dry powders, solutions in organic solvents or as dispersions. DE-A 1228685 discloses the use of a polyisobutylene solution as a binder in the electrode mass. DE-A 2354023 discloses the use of an aqueous polyisobutylene dispersion as a binder for the electrode mass of an alkaline primary element. JP-A 55050577 or JP-A 57152674 discloses the use of polytetrafluoroethylene, polyethylene or poly-styrene or salts of polyacrylic acid as binders for that purpose. Further, JP-A 04296449 discloses the use of a mixture of hydrophobic and hydophilic binders for the production of cathode bodies of alkaline primary elements.

In the case of adding organic binders to solutions, manganese dioxide and graphite particles are coated with a skin of the binder, which besides an electronic insulation effect, leads to the cathode body having hydrophobicity which is undesirable for the electrochemical release of energy. It is harder for the electrolyte to penetrate and wet the manganese dioxide particles because of this.

In the case of using dry binders in powder form, a skin-like coating on the particles contained in the electrode mass is not formed. However, even with prolonged mixing, irregular distribution of the binder and widely differing hydrophobic and hydrophilic regions in the cathode bodies are found. In particular, known binders have a tendency to fill the gaps between the electrochemically active particles in the finished electrode. The result of this is to increase the inner resistance of the cells.

Accordingly, an object of the invention is to provide a method with which it is possible to obtain positive electrode bodies that have sufficient strength and, in particular, when loaded with high currents, show an improvement in capacity.

SUMMARY OF THE INVENTION

The invention includes a process for producing a positive electrode, containing an organic polymer as binder, for primary elements with alkaline electrolytes, wherein manganese dioxide particles are mixed with a graphite dispersion, which contains an organic polymer, and are compressed to form an electrode body.

DETAILED DESCRIPTION OF THE INVENTION

It will be appreciated that the following description is intended to refer to specific embodiments selected for illustration in the Examples and is not intended to define or limit the invention, other than in the appended claims.

According to the invention, the object is achieved by a process wherein manganese dioxide particles are mixed with a graphite dispersion, which contains an organic polymer, and is compressed to form an electrode body. Advantageously, the average particle size of the graphite in the graphite dispersion is less than about 10 μm.

In a further refinement of the invention, the graphite dispersion used contains about 10 to 50% by weight graphite and about 5 to 35% by weight of an organic polymer, the remainder being a dispersion medium. In particular, the organic polymer is an amphiphilic copolymer which is selected from vinyl acetate copolymers. Of the vinyl acetate copolymers at least two groups are preferred. Examples include ethylene-vinyl acetate copolymers (E/VA) and vinyl chloride-vinyl acetate copolymers (VC/VAC) (The “slash” indicates that a copolymerizate is involved.). Generally, E/VA is considered to be an elastomer, the general structural formula of E/VA being:

Figure US06358447-20020319-C00001

An especially preferred E/VA is poly(1-acetoxyethylene-co-ethylene) or more precisely poly(ethylene-co-vinyl acetate). The properties vary depending on the length of “1” and “m” and on the number of sequences (designated as “n” above). The number for 1, m and n is at least 1.

The general structural formula of VC/VAC is:

Figure US06358447-20020319-C00002

VC/VAC is considered to be an amorphous thermoplastic. An especially preferred VC/VAC is poly(1-acetoxyethylene-co-chloroethylene) or poly(vinyl acetate-co-vinyl chloride). With respect to E/VA, the monomer content of ethylene (E) may range from about 28 to 72%, the monomer content of the vinyl acetate (VA) accordingly from about 72 to 28%. A VA monomer content of <50% is preferred since the latter produces more plastic binders.

It is also possible that the E/VA is partly cross-linked (e.g., with peroxide) in order to increase certain elastic properties of the binder. With respect to VC/VAC, the monomer content of vinyl acetate here is preferably in the range of about 5 to 20%. Furthermore, when necessary to increase metal affinity, monomer contents with about 5-10% maleic acid may be mixed in. The binders of this group may be added in smaller quantities because of their extremely soft, plastic properties, and are therefore preferred over those of the E/VA group.

An aqueous graphite dispersion is used for producing the electrode bodies, preferably about 0.5 to 3% by weight of the aqueous dispersion. Specifically, the electrode bodies are produced by mixing electrochemically purified (electrolytic) manganese dioxide (EMD) with the graphite under substantially dry conditions. The dry graphite dispersion is then injected or slowly poured into the running mixer. After a further mixing time, aqueous KOH solution is also admixed and homogenized, when appropriate.

It is also possible to add the two liquid components (graphite dispersion, KOH solution) by premixing them in the appropriate quantity ratio and then dosing them together to the dry mixture. An even better distribution of the graphite dispersion can then be obtained, depending on the mixer system employed.

The electrode mixture described above for the cathode is then rolled between compactor rolls to form a solid strip and, following this, comminuted in a granulating process to reduce it to the desired grain fraction.

The flowable “grainy” cathode mass thus produced is then compressed, for example in rotary presses, to form cathode rings or tablets in sizes depending on the type of cell.

The electrodes thus produced can in this way be processed for further insertion into the appropriate cell container. The mechanical stability of the positive electrodes prepared in this way is, with an appropriate compressed density of, for example, about 3.1-3.2 g/cm3, high enough for them to be fitted in the cell containers without damage via conveyors.

The electrode bodies produced can be used in the known way, for example to produce primary galvanic cells, by fitting them in a cell receptacle into which further KOH electrolyte (soaking electrolyte) and a zinc electrode (anode gel) are subsequently dosed with the interposition of a separator.

Unexpectedly, the electrodes produced according to the invention show outstanding load capacity in galvanic elements. Particular emphasis should be placed on the advantages in the utility of manganese dioxide (EMD) and an improvement in hard discharges, this being found to be an advantage especially after storage and, therefore, counteracting cell aging. Due to the fact that, for example, hydrophilic binders are avoided, the electrodes produced according to the invention also do not show swelling of the electrodes after further addition of the aforementioned (KOH) soaking electrolyte, which in any event, ensures straightforward and reliable cell completion in mass production.

The use according to the invention of the graphite dispersion provides excellent compressibility, reduced and less problematic premature electrode swelling (in comparison with hydrophilic binders) and an increase in capacity (in contrast to purely hydrophobic nonconductive binders).

In another variant of the application of the graphite dispersion, smaller amounts thereof are also thinly sprayed onto the already compacted and granulated grains (coating). The advantage of this is that the grains to be compressed subsequently to form the cathode on the one hand, adhere to one another better (increased in breaking strength) and, on the other hand, the bulk grain can flow more easily due to the graphite component (improvement in flowability). Further, increasing the graphite component on the grain surface provides lubrication of the pressing tools. The latter is important especially if, for example, the proportion of graphite in the mass is to be reduced further. For this extra coating process, the ratio between graphite and polymer in the graphite dispersion may be varied according to requirements and the desired effect.

Such a cathode has, for example, the following composition:

89.8% by weight EMD

5% by weight graphite

3.8% by weight KOH solution (50% strength)

1.4% by weight dispersion solution

The invention will be explained in more detail with reference to the examples below.

An evaluation was carried out with size LR6 test cells. For this purpose, annular moldings (weight 3.4 g each) with a height of 14.2 mm each and an outer diameter of 13.05 mm and an inner diameter of 8.75 mm were in each case pressed as the positive cathode 3 into a nickel-coated steel cup which was also graphite-coated on the inside.

EXAMPLE

88.15% by weight manganese dioxide

6% by weight graphite

4.5% by weight KOH solution (50% strength)

1.35% by weight dispersion solution of vinyl acetate copolymer

Comparative Example 1

(dry binder):

89% by weight manganese dioxide

6% by weight graphite

4.5% by weight KOH solution (50% strength)

0.5% by weight Sanfresh DK 300 powder

Comparative Example 2

(polyacrylic acid dispersion):

88.50% by weight manganese dioxide

6% by weight graphite

4.5% by weight KOH solution (50% strength)

1% by weight polyacrylic acid dispersion

Comparative Example 3

(polybutyl acrylate dispersion):

88.50% by weight manganese dioxide

6% by weight graphite

4.5% by weight KOH solution (50% strength)

1% by weight polybutyl acrylate dispersion

Separator: 2-layer cross winding

Soaking electrolyte 1.3 g: 38% by weight KOH solution

Negative electrode 5.2 g:

65% by weight zinc powder

0.3% by weight carboxymethyl cellulose

0.25% by weight polyacrylate

0.024% by weight indium oxide

34.426% by weight KOH solution (38% strength with 2% by weight ZnO)

The test results of the comparative tests for the various test conditions are summarized in Table 1.

Although this invention has been described in connection with specific forms thereof, it will be appreciated that a wide array of equivalents may be substituted for the specific elements described herein without departing from the spirit and scope of the invention as described in the appended claims.

TABLE 1
Comp. Ex. 2 Comp. Ex. 3
Example Comp. Polyacrylic Polybutyl
Graphite Ex. 1 acid acrylate
dispersion Dry binder dispersion dispersion
Gassing without
discharge [ml]
7MT 0.4 0.4 0.8 0.9
MT1 0.5 0.5 2.9 2.3
Gassing after
discharge [ml]
7MT 0.7 0.6 0.9 0.9
MT1 1.1 0.8 2.3 2.2
Ub-value [V]
NO 1.447 1.440 1.448 1.421
7MT 1.452 1.412 1.420 l.381
MT1 1.392 1.373 1.376 1.336
Transistor 2.51 2.52 2.49 2.42
43 Ω→0.9 V [Ah]
NO
Flash
2 Ω→1.0 V [cycles]
No 565 555 505 501
7MT 522 513 476 458
MT1 487 448 422 422
Constant discharge
3.9 Ω→0.75 V [Ah]
No 1.725 1.803 1.858 1.788
7MT 1.440 1.488 1.427 1.118
MT1 1.208 1.229 1.144 0.830
Constant current
discharge 1
A [cycles]
1.1 V 0.194 0.160 0.130 0.090
1.0 V 0.369 0.317 0.277 0.233
0.9 V 0.596 0.583 0.470 0.433

Claims (11)

What is claimed is:
1. A process for producing a positive electrode containing an organic polymer as binder for primary elements with alkaline electrolytes comprising:
spraying a graphite dispersion which contains an organic polymer on to manganese particles;
forming a rolled strip by compacting resulting sprayed particles;
breaking the strip to form granules; and
compressing the resulting mixture to form an electrode body.
2. A process for producing a positive electrode containing an organic polymer as binder for primary elements with alkaline electrolytes comprising:
spraying about 0.5-3% by weight of a graphite dispersion which contains an organic polymer on to manganese particles;
forming a rolled strip by compacting resulting sprayed particles;
breaking the strip to form granules; and
compressing the resulting mixture to form an electrode body.
3. The process as claimed in claim 1, wherein the granules are sprayed with a graphite dispersion and compressed to form electrode bodies.
4. The process as claimed in claim 1, wherein manganese dioxide particles are mixed with aqueous KOH solution, compacted to form a rolled strip and subsequently broken to form granules, and the granules are sprayed with a graphite dispersion and compressed to form the electrode bodies.
5. The process as claimed in claim 1, wherein the average particle size of the graphite in the graphite dispersion is about 10 μm.
6. The process as claimed in claim 1, wherein the graphite dispersion contains about 10-50% by weight graphite and about 5-35% by weight organic polymer.
7. The process as claimed in claim 1, wherein an amphiphilic copolymer is used as the organic polymer.
8. The process as claimed in claim 7, wherein a vinyl acetate copolymer is used as the amphiphilic copolymer.
9. The process as claimed in claim 1, wherein an aqueous graphite dispersion is used.
10. The process as claimed in claim 9, wherein about 0.5-3% by weight of the aqueous graphite dispersion is used.
11. The process as claimed in claim 1, wherein the organic polymer is selected from the group consisting of E/VA and VC/VAC.
US09429809 1998-11-02 1999-10-29 Process for the production of a positive electrode for an alkaline primary element Expired - Fee Related US6358447B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE1998150474 DE19850474A1 (en) 1998-11-02 1998-11-02 A process for producing a positive electrode for an alkaline primary element
DE19850474 1998-11-02

Publications (1)

Publication Number Publication Date
US6358447B1 true US6358447B1 (en) 2002-03-19

Family

ID=7886422

Family Applications (1)

Application Number Title Priority Date Filing Date
US09429809 Expired - Fee Related US6358447B1 (en) 1998-11-02 1999-10-29 Process for the production of a positive electrode for an alkaline primary element

Country Status (5)

Country Link
US (1) US6358447B1 (en)
EP (1) EP0999603A1 (en)
JP (1) JP2000149931A (en)
CN (1) CN1254194A (en)
DE (1) DE19850474A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6616875B2 (en) * 1999-09-16 2003-09-09 Ness Capacitor Co., Ltd. Manufacturing method for a metal oxide electrode for supercapacitor

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050064289A1 (en) * 2003-07-03 2005-03-24 Tdk Corporation Electrode, electrochemical device, method for manufacturing electrode, and method for manufacturing electrochemical device
CN102412385B (en) * 2011-09-23 2014-01-29 四川长虹电器股份有限公司 Alkaline manganese battery positive electrode body, alkaline manganese battery and its manufacturing method
JP5901356B2 (en) * 2012-03-05 2016-04-06 日立マクセル株式会社 Flat alkaline cell and a method for manufacturing the same

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3071814A (en) * 1960-05-19 1963-01-08 Guggenheim S Frederic Method and apparatus for molding
DE1228685B (en) 1963-06-28 1966-11-17 Varta Pertrix Union Ges Mit Be Depolarizer and processes for their preparation
US3737276A (en) * 1971-09-17 1973-06-05 Carborundum Co Molding of powdered or granular material
DE2354023A1 (en) 1973-10-27 1975-05-07 Varta Batterie Positive electrodes for primary cells contg. alkaline electrolyte - using insol. polymer dispersions in hydrophilic liquids as binders
JPS53124922A (en) 1977-04-06 1978-10-31 Shinko Electric Co Ltd Method of correcting read data in label reader
US4160747A (en) * 1973-10-26 1979-07-10 Varta Batterie Aktiengesellschaft Electrode and manufacturing method therefor
JPS5638200A (en) 1979-09-06 1981-04-13 Hitachi Plant Eng & Constr Co Ltd Solid-liquid separating method for anaerobic digestive slurry
US4320185A (en) * 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
US4320184A (en) * 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
JPH0363240A (en) 1989-06-13 1991-03-19 L'oreal Sa New 5,6,7,8-tetrahydro-1-naphthalenol derivative, manufacture of the same, cosmetics and medicine
US5047283A (en) * 1989-09-20 1991-09-10 Ppg Industries, Inc. Electrically conductive article
US5136371A (en) 1990-03-15 1992-08-04 Thomson Consumer Electronics, Inc. Digital image coding using random scanning
US5435874A (en) * 1993-11-01 1995-07-25 Wilson Greatbatch Ltd. Process for making cathode components for use in electrochemical cells
US5589129A (en) * 1993-02-19 1996-12-31 Kabushiki Kaisha Toshiba Method of manufacturing a molding using a filler or an additive concentrated on an arbitrary portion or distributed at a gradient concentration
US5698147A (en) * 1996-05-24 1997-12-16 W. R. Grace & Co.-Conn. Fabrication methods for low impedance lithium polymer electrodes
US5882570A (en) * 1994-06-20 1999-03-16 Sgl Technic, Inc. Injection molding graphite material and thermoplastic material
US6010653A (en) * 1997-03-19 2000-01-04 Valence Technology, Inc. Methods of fabricating electrodes for electrochemical cells

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6041829B2 (en) * 1979-01-06 1985-09-19 Hitachi Seisakusho Kk
JPH0373107B2 (en) * 1980-12-06 1991-11-20 Hitachi Maxell
CA1186373A (en) * 1982-03-29 1985-04-30 Duracell International Inc. Electrochemical cell with compacted cathode containing polyolefin powder additive
JPS59196557A (en) * 1983-04-21 1984-11-07 Matsushita Electric Ind Co Ltd Manufacture of alkaline manganese battery
JP2925589B2 (en) * 1989-08-11 1999-07-28 日立マクセル株式会社 Alkaline manganese batteries

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3071814A (en) * 1960-05-19 1963-01-08 Guggenheim S Frederic Method and apparatus for molding
DE1228685B (en) 1963-06-28 1966-11-17 Varta Pertrix Union Ges Mit Be Depolarizer and processes for their preparation
US3306781A (en) 1963-06-28 1967-02-28 Varta Pertrix Union Ges Mit Be Depolarizer mixture and molded bodies
US3737276A (en) * 1971-09-17 1973-06-05 Carborundum Co Molding of powdered or granular material
US4160747A (en) * 1973-10-26 1979-07-10 Varta Batterie Aktiengesellschaft Electrode and manufacturing method therefor
DE2354023A1 (en) 1973-10-27 1975-05-07 Varta Batterie Positive electrodes for primary cells contg. alkaline electrolyte - using insol. polymer dispersions in hydrophilic liquids as binders
JPS53124922A (en) 1977-04-06 1978-10-31 Shinko Electric Co Ltd Method of correcting read data in label reader
JPS5638200A (en) 1979-09-06 1981-04-13 Hitachi Plant Eng & Constr Co Ltd Solid-liquid separating method for anaerobic digestive slurry
US4320185A (en) * 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
US4320184A (en) * 1981-01-19 1982-03-16 Mpd Technology Corporation Production of a cell electrode system
JPH0363240A (en) 1989-06-13 1991-03-19 L'oreal Sa New 5,6,7,8-tetrahydro-1-naphthalenol derivative, manufacture of the same, cosmetics and medicine
US5047283A (en) * 1989-09-20 1991-09-10 Ppg Industries, Inc. Electrically conductive article
US5136371A (en) 1990-03-15 1992-08-04 Thomson Consumer Electronics, Inc. Digital image coding using random scanning
US5589129A (en) * 1993-02-19 1996-12-31 Kabushiki Kaisha Toshiba Method of manufacturing a molding using a filler or an additive concentrated on an arbitrary portion or distributed at a gradient concentration
US5435874A (en) * 1993-11-01 1995-07-25 Wilson Greatbatch Ltd. Process for making cathode components for use in electrochemical cells
US5882570A (en) * 1994-06-20 1999-03-16 Sgl Technic, Inc. Injection molding graphite material and thermoplastic material
US5698147A (en) * 1996-05-24 1997-12-16 W. R. Grace & Co.-Conn. Fabrication methods for low impedance lithium polymer electrodes
US6010653A (en) * 1997-03-19 2000-01-04 Valence Technology, Inc. Methods of fabricating electrodes for electrochemical cells

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6616875B2 (en) * 1999-09-16 2003-09-09 Ness Capacitor Co., Ltd. Manufacturing method for a metal oxide electrode for supercapacitor

Also Published As

Publication number Publication date Type
EP0999603A1 (en) 2000-05-10 application
CN1254194A (en) 2000-05-24 application
DE19850474A1 (en) 2000-05-04 application
JP2000149931A (en) 2000-05-30 application

Similar Documents

Publication Publication Date Title
US6022639A (en) Zinc anode for an electochemical cell
US4668596A (en) Negative electrodes for non-aqueous secondary batteries composed on conjugated polymer and alkali metal alloying or inserting material
US6207322B1 (en) Alkaline cell with semisolid cathode
US5626988A (en) Sealed rechargeable cells containing mercury-free zinc anodes, and a method of manufacture
US6849360B2 (en) Nonaqueous electrochemical cell with improved energy density
US5187033A (en) Lithium secondary battery
EP0735093A1 (en) Binder for cell and composition for electrode and cell prepared therefrom
US4556618A (en) Battery electrode and method of making
US3870564A (en) Alkaline cell
US4735875A (en) Cathodic electrode
US6040088A (en) Sodium polyacrylate gelling agent for zinc gelled anode
US6991875B2 (en) Alkaline battery including nickel oxyhydroxide cathode and zinc anode
US4853305A (en) Cathodic electrode
US3956018A (en) Primary electric current-producing dry cell using a (CFx)n cathode and an aqueous alkaline electrolyte
US5376480A (en) Alkaline battery
US5300371A (en) Manganese dioxide positive electrode for rechargeable cells, and cells containing the same
US5541022A (en) Composite anode for nonaqueous secondary battery and method for producing the same
US6300011B1 (en) Zinc/air cell
US5143805A (en) Cathodic electrode
US20060046135A1 (en) Alkaline battery with MnO2/NiOOH active material
US20060204845A1 (en) Secondary battery of improved lithium ion mobility and cell capacity
US5587254A (en) Alkaline battery having a gelled negative electrode
US20050003271A1 (en) Zinc/air cell with improved anode
WO2000013249A1 (en) Paste-like masses for electrochemical components, layers produced therefrom, and electrochemical components
US3880672A (en) Battery barrier and battery

Legal Events

Date Code Title Description
AS Assignment

Owner name: VARTA GERATEBATTERIE GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HORST-UDO, JOSE;REEL/FRAME:010570/0368

Effective date: 19991029

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Expired due to failure to pay maintenance fee

Effective date: 20100319